CN102000536B - Polyurea capsule with composite wall and high core content and preparation method thereof - Google Patents
Polyurea capsule with composite wall and high core content and preparation method thereof Download PDFInfo
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- CN102000536B CN102000536B CN2010105133548A CN201010513354A CN102000536B CN 102000536 B CN102000536 B CN 102000536B CN 2010105133548 A CN2010105133548 A CN 2010105133548A CN 201010513354 A CN201010513354 A CN 201010513354A CN 102000536 B CN102000536 B CN 102000536B
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Abstract
A preparation method of a polyurea capsule with composite wall and high core content comprises the following steps: (1) uniformly mixing 100 parts of oily substances, 10-30 parts of polyisocyanates, 8-25 parts of styrene, 3-5 parts of divinylbenzene and 0.1-0.3 parts of initiator azodiisobutyronitrile or benzoyl peroxide to prepare oil phase; dropwise adding the oil phase to 500-1200 parts by weight of emulsifier aqueous solution with concentration of 1-10wt% and stirring the mixture at high speed to fully emulsify the oil phase to prepare O/W emulsion; (2) stirring the emulsion at 100-1000rpm and simultaneously dropwise adding 500-1100 parts by weight of polyamine aqueous solution with concentration of 2-5wt% to the emulsion; and (3) after dropwise adding the polyamine aqueous solution, raising the temperature to 30-60 DEG C and maintaining the temperature for 1-3hr; then raising the temperature to 75-95 DEG C and curing the mixture for 1-3hr and obtaining the capsule powder through pumping filtration, washing and drying. The capsule has the following advantages: the capsule adopts the reactive monomer as the cosolvent or adds the substance with the same functions as the core to serve as the cosolvent to replace the traditional organic cosolvent with low boiling point, has core content as high as 60-90wt% and avoids harms to human and the environment caused by using the organic solvent.
Description
Technical field
The present invention relates to high capsule-core content polyureas capsule and processing and preparing technology thereof, in particular a kind of is the preparation method and products thereof of the phase-change accumulation energy capsule of main clad material with polyureas.
Background technology
Capsule is the closed type particulate that makes with protectiveness wall materials such as organic material, inorganic material or metal material parcel core materials, is mainly used in the mode of appearance or the character of regulating or changing original capsule-core material.For example: the phase-change accumulation energy capsule has been realized the permanent solid state of phase-change material, solved phase-change material leakage and with problems such as the material around interface combines, prolonged material service life, make the more convenient application of phase-change material.Microcapsules (particle diameter is from 1 micron to 1 millimeter) technology just has been used for the pressure-sensitive NCR in the 1950's; Progress along with capsule technique; Not only develop the Nano capsule of particle diameter, and the range of application of microcapsules industries such as medicine, food, agricultural chemicals, feed, coating, adhesive, cosmetics, printing ink, textile dyeing and finishing have been expanded to from initial NCR in nanometer range.
Adopt interfacial polymerization to prepare the polyureas capsule many advantages are arranged: technology is simple, and reaction speed is fast, can carry out at normal temperatures, and is low for equipment requirements etc.The preparation of relevant polyureas capsule has patent, bibliographical information more; Its major technique approach is that the lower boiling material of employing is that cosolvent is mixed into the homogeneous oil phase with capsule-core and polyisocyanates; Then in the aqueous phase stirring and emulsifying; Drip the water-based reaction monomers again, make it interfacial polymerization take place and generate capsule on oil phase emulsion droplet surface.The use of low boiling cosolvent has reduced effective capsule-core content, also can produce certain influence to capsule performance, environment etc. simultaneously.
2007, Chinese patent CN101029215A announced a patent of invention-" preparation method of energy-storing polyurethane microcapsule " of Hua Mingyang, and through interfacial polymerization, having prepared with the n-alkane is that capsule-core, polyurethane are the accumulation energy microcapsule of cyst wall in the patent.Concrete scheme is following: oil phase is made up of polyisocyanates 5～6 weight portions, n-alkane 20～25 weight portions and cyclohexane 20～30 weight portions; Water is made up of NaOH 0.3～0.5 weight portion, sodium alginate 0.3～0.5 weight portion and deionized water 200 weight portions; Preparation technology is that in above-mentioned oil phase, to add ethylene glycol an amount of with deionized water, mixes the back and under stirring action, being added dropwise to aqueous phase, reacts at a certain temperature to make micron powder.Because n-alkane becomes the homogeneous oil phase with the polyisocyanates unmixing, needing to add considerable cyclohexane give is cosolvent, and the content of capsule-core n-alkane is on the low side in the microcapsules of preparation thus, and the energy storage effect is bad.In addition; Hua Mingyang is in patent CN1936170A-" preparation method of polyurethane fragrant microcapsules "; Adopt the similar method to have prepared the polyurethane microcapsule that contains essence, oil phase has used almost the cyclohexane give with the essence equivalent to be cosolvent equally, and this just greatly reduces the content of capsule-core material-essence; Simultaneously, the use of organic cosolvent also has certain influence to environment, the performance of essence microcapsule own such as intensity, fragrance etc.
2006; Chinese patent CN1736575A has announced people's such as Li Gang patent-" preparation method of bilayered microcapsule of polyurea-urea formaldehyde resin "; Adopt interfacial polymerization to prepare polyurea microcapsule in the patent, adopt situ aggregation method then, preparation is that capsule-core, Lauxite are the polyureas-urea aldehyde bilayered microcapsule of cyst wall with the polyurea microcapsule; The transparent rounding of capsule has good intensity, toughness, acid resistance and sealing.It is capsule-core with the hexadecane that Chinese patent-" polyurea-melamin resin double-wall material cetane microcapsule and preparation method thereof " (CN1736575A, 2009) then announced a kind of, and polyureas is that internal layer cyst wall, melamine resin are the microcapsule preparation method of outer cyst wall.In these two patents about double-deck cyst wall microcapsules; Formaldehyde has all been used in the preparation that outer cyst material is Lauxite (urea-copolyoxymethylenes) and melamine resin (carbamide copolymer); Residual formaldehyde still can't be removed at present fully, and this will certainly work the mischief to environment and human health.
The polyureas capsule has advantages such as high efficiency, low cost, preparation technology are simple, has bright application prospect.But in practical application, also have problems such as capsule-core content is on the low side, cosolvent is residual, it is necessary that the polyureas capsule is carried out modification.In applicant's range of search; Adopt polyisocyanates and polyamine; Adopting the material with reactive monomer molecule (like styrene, divinylbenzene etc.) or employing and capsule-core identical function simultaneously is cosolvent, and the research for preparing high capsule-core content polyureas capsule aspect does not also appear in the newspapers.
Summary of the invention
For overcome existing with the polyureas be the microcapsules capsule-core content of cyst wall low with problems such as organic cosolvent is residual; The invention provides a kind of material with reactive monomer or interpolation and capsule-core identical function is the preparation method of the compound cyst wall capsule of polyureas of cosolvent (promptly common alleged organic cosolvent), high capsule-core content, and the capsule product of this method preparation.
The preparation method of the compound cyst wall capsule of polyureas of the high capsule-core content of the present invention comprises following step:
(1). 100 weight portion oily matters, 10～30 weight portion polyisocyanates, 8～25 parts by weight of styrene and 3～5 weight portion divinylbenzenes are mixed make oil phase;
This oil phase is added drop-wise in the emulsifier aqueous solution of 500～1200 weight portions of concentration 1～10wt%, at room temperature, fully emulsified, makes the O/W emulsion with 3000～8000rpm high-speed stirred;
(2). stir this O/W emulsion with 100～1000rpm speed, the polyamine aqueous solution with 500～1100 weight portions of concentration 2～5wt% is added drop-wise in this O/W emulsion simultaneously;
(3). after dropwising, be warming up to 30～60 ℃, keep 1～3hr; Be warming up to 75～95 ℃ of slaking 1～3hr then,, obtain capsule powders through suction filtration, washing, drying.
In step (1) the preparation oil phase, can add oil-soluble part initator of 0.2～0.5 weight portion, this oil-soluble part initator is selected azodiisobutyronitrile or benzoyl peroxide etc. for use.
A kind of preparation method of polyureas cyst wall capsule of high capsule-core content comprises following step:
A. 100 weight portion oily matters, 10～30 weight portion polyisocyanates and 10～15 weight portion fatty acid esters are mixed and make oil phase;
This oil phase is added drop-wise in the emulsifier aqueous solution of 500～1200 weight portions of concentration 1～10wt%, at room temperature, makes the O/W emulsion with the emulsification of 3000～8000rpm high-speed stirred;
B. under 100～1000rpm speed, stir this O/W emulsion, 500～1100 weight portion polyamine aqueous solution with concentration 2～5wt% are added drop-wise in this O/W emulsion simultaneously;
C. after dropwising, be warming up to 30～60 ℃, keep 1～3hr; Through suction filtration, washing, drying, obtain capsule powders.
The compound cyst wall capsule of a kind of styrol copolymer-polyureas that the inventive method makes; It is characterized in that: this capsule is single nucleocapsid structure; Particle diameter is 5～30 μ m, is cyst wall with styrol copolymer-polyureas compound, and wall thickness is less than 300nm; Capsule-core is an oily matter, and the capsule-core effective content is 60～90wt%.
In the said method, said oily matter comprises paraffin class material, chlorinated paraffin wax class material, fatty alcohol, aliphatic acid, fatty acid ester, essence or spices.Said aliphatic hydrocarbon is preferably C
14～C
50Alkane in any or its combination in any, especially be preferably the tetradecane, hexadecane, octadecane, eicosane, No. 25 phase transformation paraffin, No. 30 phase transformation paraffin; Said fatty alcohol is preferably lauryl alcohol, tetradecyl alchohol, hexadecanol, 18 alcohol, cyclohexanol, the tert-butyl alcohol, 2, amino-2 methyl isophthalic acids of 2-dimethyl 1,3 propane diols or 2-, 3 glycerine; Said aliphatic acid is preferably capric acid, laurate, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid or octadecanoid acid; Or two or more mixture of above-mentioned organic compound, but be not limited thereto the material that list in the place.Essence or spices comprise rose sesame oil, cypress essence etc.
Said fatty acid ester adopts butyl octadecanoate, hexadecanoic acid butyl ester or tetradecanoic acid butyl ester etc.
Said polyisocyanates adopts toluene di-isocyanate(TDI), isoflurane chalcone diisocyanate or '-diphenylmethane diisocyanate etc.
Said emulsifying agent is selected styrene maleic anhydride copolymer, polyvinyl alcohol, polyvinylpyrrolidone etc. for use, but is not limited thereto.
Said water-soluble polyamine comprises ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, TEPA etc.
The capsule grain diameter scope that the present invention is suitable for is restriction not, generally can be from 10 nanometers to 10 millimeter, and scope is from 50 nanometers to 1 millimeter preferably.
It is that the material of cosolvent or interpolation and capsule-core identical function is a cosolvent that the present invention adopts reactive monomer, prepares the compound cyst wall capsule of styrol copolymer-polyureas of high capsule-core content, compared with prior art, has following obvious advantage:
It adopts reactive monomer is that the material of cosolvent or interpolation and capsule-core identical function is a cosolvent; Replace traditional low boiling organic cosolvent; Improved the capsule-core effective content greatly, simultaneously, avoided of the harm of the organic solvent (like cyclohexane, acetone etc.) of traditional use human and environment.
The capsule of the compound cyst wall of styrol copolymer-polyureas that the present invention makes has strengthened the mechanical strength of capsule greatly; Capsule-core is an oily matter, and the capsule-core effective content is up to 60～90wt%.
Description of drawings
What Fig. 1 made for the embodiment of the invention 1 is the phase-change accumulation energy capsule enlarged photograph of cyst wall with styrol copolymer-polyureas composite;
Fig. 2 is the ruptured capsules photo in the compound cyst wall capsule of Fig. 1 styrol copolymer-polyureas;
Fig. 3 is for being the capsule DSC curve of capsule-core with phase-changing energy storage material-octadecane.
The specific embodiment
Further specify below in conjunction with embodiment.
1. prepare oil phase, water A and aqueous phase B
With toluene di-isocyanate(TDI) 3.0g, styrene 2.5g, divinylbenzene 0.5g, azodiisobutyronitrile 0.05g and n-octadecane 10.0g mix, and make oil phase.
Styrene-maleic anhydride copolymer 4.0g is dissolved in distilled water 100.0g, makes water A (being emulsifier aqueous solution).
The 3.0g diethylenetriamine is dissolved in the 100.0g distilled water, makes aqueous phase B.
2. oil-phase solution is dripped or pours in the water A solution, high-speed stirred emulsification is 10 minutes under 35 ℃, 4000 rev/mins conditions, makes the O/W emulsion.
3. stir the O/W emulsion with 400rpm speed, drip aqueous phase B solution simultaneously to the O/W emulsion.
4. after dropwising, be warming up to 50 ℃, continue reaction 3.0hr.
5. be warming up to 85 ℃, reaction and slaking 3.0hr.
6. the capsule that makes of suction filtration, washing, drying, product is a pale yellow powder, particle diameter is at 5～20 μ m.
From Fig. 3 with phase-changing energy storage material---octadecane is the capsule DSC curve of capsule-core, can find out, the heat content that the fusion of capsule absorbs is 173.66J/g; Melt temperature is 38.12 ℃; The enthalpy that crystallization discharges is 168.24J/g, and crystallization temperature is 15.43 ℃, has energy storage effect preferably.According to the ratio of capsule evenly heat enthalpy (171.7J/g) with corresponding pure octadecane heat enthalpy value (231.7J/g), the capsule-core content that can draw capsule is about 73.8wt%.
Adopt the hot property of differential scanning calorimeter resolution chart 1 phase-change accumulation energy capsule, the melt phase change temperature is about 35 ℃, and the average phase change enthalpy is about 170J/g, and capsule capsule-core content is about 75wt%.It is thus clear that the effective content of the capsule-core n-octadecane of the capsule that embodiment 1 makes improves greatly, and mechanical strength increases.
1. prepare oil phase, water A and aqueous phase B
With toluene di-isocyanate(TDI) 20.0g, n-octadecane 70.0g, butyl octadecanoate 10.0g mixes, and makes oil phase.
Styrene-maleic anhydride copolymer 30.0g is dissolved in distilled water 700.0g, makes water A.
The 15.0g TEPA is dissolved in the 300.0g distilled water, makes aqueous phase B.
2. oil-phase solution is dripped or pours in the water A solution, high-speed stirred emulsification is 10 minutes under 35 ℃, 4000 rev/mins conditions, makes the O/W emulsion.
3. stir the O/W emulsion with 600rpm speed, drip aqueous phase B solution simultaneously to the O/W emulsion.
4. after dropwising, be warming up to 50 ℃, continue reaction 3.0hr.
5. the capsule that makes of suction filtration, washing, drying, product is the pale powder, particle diameter is at 5～30 μ m.
Embodiment 3
1. prepare oil phase, water A and aqueous phase B
With toluene di-isocyanate(TDI) 5.0g, styrene 3.5g, divinylbenzene 1.5g, benzoyl peroxide 0.08g, flavoring rose essence 40.0g mixes, and makes oil phase.
Styrene-maleic anhydride copolymer 10.0g is dissolved in distilled water 200.0g, makes water A.
The 5.0g hexamethylene diamine is dissolved in the 100.0g distilled water, makes aqueous phase B.
2. oil-phase solution is poured in the water A solution, at room temperature, high-speed stirred emulsification made the O/W emulsion in 10 minutes under 8000 rev/mins of conditions.
3. stir the O/W emulsion with 400rpm speed, drip aqueous phase B solution simultaneously to the O/W emulsion.
4. after dropwising, be warming up to 50 ℃, continue reaction 3.0hr.
5 are warming up to 85 ℃ again, reaction and slaking 3.0hr.
6. the capsule that makes of suction filtration, washing, drying, product is a pale yellow powder, particle diameter is at 5～10 μ m.
The inventive method can make a kind of compound cyst wall capsule of styrol copolymer-polyureas of high capsule-core content; This capsule is single nucleocapsid structure, and particle diameter is 0.1～1000 μ m, is cyst wall with styrol copolymer-polyureas compound; Capsule-core is an oily matter, and the capsule-core effective content is 60～90wt%.
Wherein, said oily matter comprises paraffin class material, chlorinated paraffin wax class material, fatty alcohol, aliphatic acid, fatty acid ester, essence or spices.
Claims (8)
1. the preparation method of the compound cyst wall capsule of the styrol copolymer-polyureas of a high capsule-core content is characterized in that comprising following step:
(1). 100 weight portion oily matters, 10～30 weight portion polyisocyanates, 8～25 parts by weight of styrene and 3～5 weight portion divinylbenzenes are mixed make oil phase; Wherein, said oily matter is paraffin, chlorinated paraffin wax, fatty alcohol, aliphatic acid, fatty acid ester or spices;
This oil phase is added drop-wise in the emulsifier aqueous solution of 500～1200 weight portions of concentration 1～10wt%, at room temperature, fully emulsified, makes the O/W emulsion with 3000～8000rpm high-speed stirred;
(2). stir this O/W emulsion with 100～1000rpm speed, the polyamine aqueous solution with 500～1100 weight portions of concentration 2～5wt% is added drop-wise in this O/W emulsion simultaneously;
(3). after dropwising, be warming up to 30～60 ℃, keep 1～3hr; Be warming up to 75～95 ℃ of slaking 1～3hr then,, obtain capsule powders through suction filtration, washing, drying.
2. method according to claim 1 is characterized in that: in step (1) the preparation oil phase, add oil-soluble part initator of 0.2～0.5 weight portion, this oil-soluble part initator is selected azodiisobutyronitrile or benzoyl peroxide for use.
3. method according to claim 1 and 2 is characterized in that: said polyisocyanates is toluene di-isocyanate(TDI), isoflurane chalcone diisocyanate or '-diphenylmethane diisocyanate.
4. method according to claim 1 and 2 is characterized in that: said emulsifying agent is styrene maleic anhydride copolymer, polyvinyl alcohol or polyvinylpyrrolidone.
5. method according to claim 1 and 2 is characterized in that: the said polyamine aqueous solution is the aqueous solution that contains ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine or TEPA.
6. the preparation method of the polyureas cyst wall capsule of a high capsule-core content is characterized in that comprising following step:
A. 100 weight portion oily matters, 10～30 weight portion polyisocyanates and 10～15 weight portion fatty acid esters are mixed and make oil phase; Wherein, said oily matter is paraffin, chlorinated paraffin wax, fatty alcohol, aliphatic acid or fatty acid ester;
This oil phase is added drop-wise in the emulsifier aqueous solution of 500～1200 weight portions of concentration 1～10wt%, at room temperature, makes the O/W emulsion with the emulsification of 3000～8000rpm high-speed stirred;
B. under 100～1000rpm speed, stir this O/W emulsion, the 500-1100 weight portion polyamine aqueous solution with concentration 2～5wt% is added drop-wise in this O/W emulsion simultaneously;
C. after dropwising, be warming up to 30～60 ℃, keep 1～3hr; Through suction filtration, washing, drying, obtain capsule powders.
7. method according to claim 6 is characterized in that: said fatty acid ester is selected butyl octadecanoate, hexadecanoic acid butyl ester or tetradecanoic acid butyl ester for use; Said emulsifying agent is selected styrene maleic anhydride copolymer, polyvinyl alcohol or polyvinylpyrrolidone for use; Said polyisocyanates is selected toluene di-isocyanate(TDI), isoflurane chalcone diisocyanate or '-diphenylmethane diisocyanate for use.
8. according to claim 6 or 7 described methods, it is characterized in that: the said polyamine aqueous solution is the aqueous solution that contains ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine or TEPA.
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| CN104789355B (en) * | 2015-04-15 | 2018-05-11 | 上海爱文斯顿新材料科技有限公司 | The polyurea shell essence microcapsule of a kind of surface with positive charge and preparation method thereof |
| CN107096475B (en) * | 2017-05-09 | 2021-01-19 | 西安工程大学 | Phase change microcapsule with polyurethane reticular structure and preparation method thereof |
| CN108041674B (en) * | 2017-11-29 | 2020-12-18 | 武汉纺织大学 | A kind of high-efficiency water-blocking and anti-penetration capsule and preparation method thereof |
| CN108057402A (en) * | 2018-02-02 | 2018-05-22 | 成都优创复材科技有限公司 | A kind of method for preparing the microcapsules containing pure polyamine and its microlayer model makeup are put |
| WO2019148577A1 (en) * | 2018-02-02 | 2019-08-08 | 成都优创复材科技有限公司 | Method for preparing microcapsule containing pure polyamine and microdroplet forming device thereof |
| CN108896434B (en) * | 2018-09-28 | 2020-08-25 | 武汉理工大学 | Measurement method of core content of self-healing capsules |
| CN113773808B (en) * | 2021-07-28 | 2023-11-17 | 浙江理工大学 | A high latent heat energy storage microcapsule based on reactive phase change core material and its preparation method |
| CN114058204B (en) * | 2022-01-14 | 2022-04-29 | 虎丘影像(苏州)股份有限公司 | Fluorine-containing thermosensitive dye microcapsule, preparation method thereof and film |
| CN114989786B (en) * | 2022-06-09 | 2023-08-15 | 纯钧新材料(深圳)有限公司 | Sarin resin phase-change microcapsule and preparation method thereof |
| CN115353671B (en) * | 2022-09-14 | 2024-03-22 | 山东润义金新材料科技股份有限公司 | High-tightness dimethyl methylphosphonate flame retardant microcapsule and preparation method thereof |
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| CN101045857A (en) * | 2006-03-30 | 2007-10-03 | 北京汇林盛达能源材料科技发展有限公司 | Preparation method of phase transformation material microcupsule |
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| WO2010042566A1 (en) * | 2008-10-08 | 2010-04-15 | Microtek Laboratories, Inc. | Microencapsulation of a phase change meterial with enhanced flame resistance |
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| CN101045857A (en) * | 2006-03-30 | 2007-10-03 | 北京汇林盛达能源材料科技发展有限公司 | Preparation method of phase transformation material microcupsule |
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| 一种致密的相变储能微胶囊的制备与表征;叶玉花 等;《应用化学》;20071130;第24卷(第11期);1318-1321 * |
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